Methods for controlling pests with substituted phenyl thio(thiono)phosphates and the thio(thiono)phosphates

ABSTRACT

Novel phosphorous esters of substituted phenols have been found to exhibit insecticidal and miticidal activity.

This invention relates to novel insecticidal and miticidal phosphorousesters of substituted phenols. This invention also relates to pesticidalcompositions for controlling insects and mites, as well as to methods ofcontrolling insects and mites by subjecting them to an insecticidally ormiticidally effective amount of a compound of this invention.

The novel compounds of this invention are compounds of the formula:##STR1## wherein: X is oxygen or sulfur;

R¹ and R² are individually lower alkyl groups;

Z is hydrogen, alkyl, alkoxy, halo, nitro, cyano, aryl, aryloxy,alkylthio, amino, alkylamino, dialkylamino, a C₃ to C₈ cycloalkyl,alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylaminoalkyl,dialkylaminoalkyl, trihaloalkyl, or divalent alkylene group of 3 to 5carbon atoms wherein the formed 6-membered ring may optionally bearomatic or substituted aromatic;

n is 1, 2 or 3;

Y is: ##STR2## wherein: R³ and R⁴ are individually hydrogen, loweralkyl, lower alkenyl, or aryl;

3. NOR⁵

wherein:

R⁵ is substituted or unsubstituted lower alkyl, aryl, or arylalkyl;##STR3## wherein: R⁶ is lower alkyl, alkoxy, aryloxy, substituted alkyl,cycloalkyloxy, furanyl, or phenylureido;

5. oxygen;

6. CR⁷ R⁸

wherein:

R⁷ and R⁸ are hydrogen, alkyl, cyano, or halo; ##STR4## wherein: R⁹ islower alkyl;

wherein:

X¹ is oxygen or sulfur;

with the proviso that when Y is oxygen, Z is not a lower alkyl, halo, orhydrogen.

Generally, the preferred compounds of this invention are those

wherein:

R¹ is ethyl;

R² is n-propyl;

Y is ##STR5## Z is hydrogen, a 4 carbon, divalent alkylene group forminga 6-membered aromatic ring or halo;

n is 1, 2 or 3; and

X is oxygen.

The most preferred compounds of this invention are the following:

O-ethyl-S-n-propyl-O-[1-(semicarbazono-methyl)-2-naphthyl]-thiophosphate;

O-ethyl-S-n-propyl-O-[2-(semicarbazono-methyl)phenyl]-thiophosphate;

O-ethyl-S-n-propyl-O-[2-(acetylhydrazonomethyl)phenyl]-thiophosphate;

O-ethyl-S-n-propyl-O-[2-(methoxycarbonyl-hydrazonomethyl)phenyl]thiophosphate;

O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminomethyl)phenyl]thiophosphate;and

O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosphate.

O-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyloxyiminomethyl)phenyl]thiophosphate.

O-ethyl-S-n-propyl-O-[2,6-dibromo-4(methoxyiminomethyl)phenyl]thiophosphate.

The novel phosporous esters of substituted phenols of this invention canbe conveniently prepared by the two general reaction methods ormodifications thereof set forth below: ##STR6##

In these reaction sequences one equivalent of the parent phenol reactswith an appropriate chlorophosphorous compound in the presence of atleast one equivalent of an acid acceptor (base), preferably in an inertsolvent. The aldehyde is reacted with at least one equivalent of YH₂ inan inert solvent.

In general any organic solvent that is inert to the reactants orreaction conditions may be employed in the reaction schemes shown above.Illustrative solvents which are suitable in the phosphorylation reactionare saturated, unsaturated, and aromatic hydrocarbons, e.g., hexane,cyclohexane, octane, cyclohexene, dodecane, naphtha, decalin, kerosene,cycloheptane, benzene, toluene, xylene, naphthalene, or the like; etherssuch as dioxane, tetrahydrofuran, diethyl ether, tetrahydropyran,1,2-dimethoxybenzene, the dialkyl ethers of ethylene glycol, ofpropylene glycol, or chlorinated aliphatic hydrocarbons such aschloroform, dichloromethane, 1,1-di-chloroethane, carbon tetrachloride,and the like.

The phosphorylation reactions may also be conducted in a solvent whichfunctions as an acid acceptor. Illustrative of such solvents areN,N-dimethylaniline, pyridine, alpha-picoline, any lutidine, collidineor similar aromatic or hetero-cyclic tertiary amine compound.

In general solvents used to effect condensation (--CHO→--CH═Y) includewater, ethers such as dioxane, tetrahydrofuran, dialkyl ethers ofethylene glycol, alcohols--such as methanol, ethanol, isopropanol,esters such as ethyl acetate and combinations thereof.

The acid acceptor utilized in these reactions can be either organic orinorganic bases. Illustrative of organic bases that are useful acidacceptors are tertiary amines such as triethylamine, pyridine,trimethylamine, 4-dimethylaminopyridine, or1,4-diazabicyclo[2.2.2]octane; bases such as sodium carbonate, potassiumcarbonate, sodium acetate, and sodium hydroxide are illustrative ofuseful inorganic bases.

The reactions set forth above are neither temperature nor pressuresensitive and can be conducted over a broad range of temperatures andpressures to yield the desired product. Preferably these reactions areconducted at a temperature of from about -40° C. to about 140° C. and atatmospheric or autogeneous pressure.

The phosphorous halides utilized as reactants in the above schemesgenerally are known materials in the art and can be obtained fromcommercial sources or prepared in accordance with conventional methodsknown to those skilled in the art.

The substituted phenols utilized as starting materials in the aboveschemes are known compounds or can be prepared in accordance withconventional methods known to those skilled in the art.

The following examples are illustrative of the methods of preparing thenovel compounds of this inventions.

EXAMPLE I Preparation ofO-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphate

A 100 ml four-neck round bottom flask, equipped with a magnetic stirringbar, water condenser, and thermometer, was charged with 3.7 grams (0.03mole) salicyaldehyde, 4.0 grams (0.04 mole) triethylamine and 50 mlanhydrous ether. The resulting solution was stirred at room temperatureduring which time 5.9 grams (0.029 mole) o-ethyl-S-n-propylphosphorochloridate was added dropwise. The material was stirred untilthe reaction was complete at which time the resulting precipitate wasfiltered. The ether layer was washed with water, dried over anhydrousmagnesium sulfate, filtered and concentrated to yield the substitutedphenol phosphate.

1.3 grams (0.0115 mole) of semicarbazide hydrochloride; 1.25 g (0.015mole) sodium acetate; and 10 ml of water was added to a 250 mlErlynmeyer flask. The contents were heated to 57° C. at which time 2.5 g(0.0085 mole) O-ethyl-S-n-propyl-O-[2-formylphenyl]thiophosphatedissolved in 5 ml of ethyl alcohol was added. The precipitate wasfiltered, washed with water, acetone, and ethyl ether. The material wasthen dried in a vacuum oven to yield 1.2 g (40.9Δ yield) of producthaving a melting point of 127°-129° C.

Calcd. for C₁₃ H₂₀ N₃ O₄ PS: C, 45.22; H, 5.80. Found: C, 45.36; H,5.72.

EXAMPLE II Preparation ofO-ethyl-S-n-propyl-O-[4-(methoxyiminomethyl)-phenyl]thiophosphate

Methoxyamine hydrochloride (4.93 g, 59 mmol), sodium acetate (5.55 g, 66mmol) and water (20 ml) were warmed to 50° C. and a solution ofO-ethyl-S-n-propyl-O-(4-formylphenyl)thiophosphate (11.39 g, 39.5 mmol)in ethanol (10 ml) was added at once. The solution was cooled to roomtemperature. After 3 hours, the solution was diluted with water (100 ml)and extracted three times with ethyl acetate. The combined organicextracts were washed once with water and dried over magnesium sulfate.Filtration and concentration under reduced pressure afforded the desiredproduct: 9.63 g yellow oil.

Calcd. for C₁₃ H₂₀ NO₄ PS: C, 49.20; H, 6.35. Found: C, 49.35; H, 6.42.

The following compounds are illustrative of this invention all of whichcan be conveniently prepared by the processes of this invention simplyby selecting appropriate starting materials.

O-ethyl-S-n-propyl-O-[3-(isopropoxycarbonylhydrazonomethyl)-phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(n-propyloxycarbonylhydrazonomethyl)-phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-chloro-3-(ethoxycarbonylhydrazono-methyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[3-chloro-5-(methoxycarbonylhydrazono-methyl)phenyl]dithiophosphate

O-ethyl-S-n-propyl-O-[4-chloro-2-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-nitro-2-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-methoxy-4-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-(methoxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-nitro-3-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-methoxy-6-nitro-4-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(t-butoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-(2-formyl-4-nitrophenyl)thiophosphate

O-ethyl-S-n-propyl-O-(3-formyl-4-nitrophenyl)thiophosphate

O-ethyl-S-n-propyl-O-(4-formyl-2-methoxy-4-nitrophenyl)thiophosphate

O-ethyl-S-n-propyl-O-(4-formyl-3-methoxyphenyl)thiophosphate

O-ethyl-S-n-propyl-O-(1-formyl-2-naphthyl)thiophosphate

O-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)-2-naphthyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-chloro-1-(semicarbazonomethyl)-2-naphthyl]thiophosphate

O-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)-2-(5',6',7',8'-tetrahydronaphthyl)]thiophosphate

O-ethyl-S-n-propyl-O-[1-(1'-semicarbazonoethyl)-2-naphthyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-butyl-O-[1-formyl-2-naphthyl)thiophosphate

O-ethyl-S-n-propyl-O-[1-(thiosemicarbazonomethyl)-2-naphthyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(thiosemicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(2',2'-dicyanovinyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(trimethylammoniumacetylhydrazonomethyl)phenyl]thiophosphatechloride

O-ethyl-S-n-propyl-O-[4-(1'-methoxyiminoethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-(1'-ethoxycarbonylhydrazonoethyl)phenyl]thiophosphate

O-ethyl-S-n-butyl-O-[2-chloro-4-(1'-ethoxycarbonylhydrazonoethyl)phenyl]thiophosphate

O-ethyl-S-n-butyl-O-[4-(2',2'-dicyanovinyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminoethyl)phenyl]-thiophosphate

O-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyloxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-phenyl-O-[2,6-dibromo-4-(methoxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-nitro-2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-chloro-2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-nitro-2-(methoxyminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-chloro-2-(methoxyminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-nitro-2-(acetylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-chloro-2-(acetylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-(oxamoylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-(1-methoxyiminomethyl-2-naphthyl)thiophosphate

O-ethyl-S-n-propyl-O-[4-methoxy-2-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-methoxy-2-(acethylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-methoxy-2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-methoxy-2-(methoxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(oxamoylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(methoxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(ethoxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-chloro-4-(methoxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-(methoxyiminomethyl)phenyl]dithiophosphate

O-ethyl-S-n-butyl-O-[4-(methoxyiminomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[3-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-butyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[4-(thiosemicarbazonomethyl)phenyl]dithiophosphate

O-ethyl-S-n-propyl-O-[2,6-dichloro-3-(semicarbazonomethyl)-phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-chloro-3-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(acetylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(cyanoacetylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(2-furoylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-propyl-O-[2-(ethoxycarbonylhydrazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-butyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosphate

O-ethyl-S-n-butyl-O-[4-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate

Selected species of the new compounds were evaluated to determine theirpesticidal activity against mites, mite eggs, an aphid, a caterpillar, abeetle, and a fly.

Suspensions of the test compounds were prepared by dissolving one gramof compound in 50 ml of acetone in which had been dissolved 0.1 g (10percent of the weight of the compound) of an alkylphenoxypolyethoxyethanol surfactant, as an emulsifying or dispersing agent. Theresulting solution was mixed into 150 ml of water to give roughly 200 mlof a suspension containing the compound in finely divided form. Thethus-prepared stock suspension contained 0.5 percent by weight ofcompound. The concentrations in parts per million by weight employed inthe tests described hereinbelow were obtained by appropriate dilutionsof the stock suspension with water. The test procedures were as follows:

Bean Aphid Foliage Spray Test

Adults and nymphal stages of the bean aphid (Aphis fabae Scop.) rearedon potted dwarf nasturtrium plants at 68°-70° F. and 50±5 percentrelative humidity, constituted the test insects. For testing purposes,the number of aphids per pot was standardized to 100-150 by trimmingplants containing excess aphids.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation.

The potted plants (one pot per compound tested) infested with 100-150aphids were placed on a revolving turntable and sprayed with 100-110milliliters of test compound formulation by use of a DeVilbiss spray gunset at 40 psig air pressure. This application, which lasted 25 seconds,was sufficient to wet the plants to run-off. As a control, 100-110milliliters of a water-acetone-emulsifier solution containing no testcompound were also sprayed on infested plants. After spraying, the potswere placed on their sides on a sheet of white standard mimeograph paperwhich had been previously ruled to facilitate counting. Temperature andhumidity in the test room during the 24 hour holding period were 68°-70°F. and 50±5 percent, respectively. Aphids which fell onto the paper andwere unable to remain standing after being uprighted were considereddead. Aphids remaining on the plant were observed closely for movementand those which were unable to move the length of the body uponstimulation by prodding were considered dead. Percent mortality wasrecorded for various concentration levels.

Southern Armyworm Leaf Spray Bait Test

Larvae of the southern armyworm (Spodoptera eridania, (Cram.)), rearedon Tendergreen bean plants at a temperature of 80+5° F. and a relativehumidity of 50±5 percent, constituted the test insects.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation. Potted Tendergreen bean plants ofstandard height and age were placed on a revolving turntable and sprayedwith 100-110 milliliters of test compound formulations by use of aDeVilbiss spray gun set at 40 psig air pressure. This application, whichlasted 25 seconds, was sufficient to wet plants to run-off. As acontrol, 100-110 milliliters of a water-acetone-emulsifier solutioncontaining no test compound were also sprayed on infested plants. Whendry, the paired leaves were separated and each one was placed in a 9centimeter Petri dish lined with moistened filter paper. Five randomlyselected larvae were introduced into each dish and the dishes wereclosed. The closed dishes were labeled and held at 80°-85° F. for threedays. Although the larvae could easily consume the whole leaf withintwenty-four hours, no more food was added. Larvae which were unable tomove the length of the body, even upon stimulation by prodding, wereconsidered dead. Percent mortality was recorded for variousconcentration levels.

Mexican Bean Beetle Leaf Spray Test

Fourth instar larvae of the Mexican bean beetle (Epilachna varivestis,Muls.), reared on Tendergreen bean plants at a temperature of 80±5 F.and 50±5 percent relative humidity, were the test insects.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation. Tendergreen bean plants of standardheight and age were placed on a revolving turntable and sprayed with100-110 milliliters of test compound formulation by use of a DeVilbissspray gun set at 40 psig air pressure. This application, which lasted 25seconds, was sufficient to wet plants to run-off. As a control, 100-110milliliters of a water-acetone-emulsifier solution containing no testcompound were also sprayed on infested plants. When dry, the pairedleaves were separated and each was placed in a 9 centimeter Petri dishlined with moistener filter paper. Five randomly selected larvae wereintroduced into each dish, and the dishes were closed. The closed disheswere labeled and held at a temperature of 80+5 F., for three days.Although the larvae could easily consume the leaf within 24 to 48 hours,no more food was added. Larvae which were unable to move the length ofthe body, even upon stimulation, were considered dead.

Southern Armyworm Ovicide Test

The test organism was the egg of the Southern armyworm (Spodopteraeridania (Cram.)) as obtained from adults reared on Tendergreen beanplants at a temperature of 80°±5° F. and a relative humidity of 50±5percent. The eggs were laid on freezer paper (Marlon 717, Copco paper).The paper was then cut into small sections containing one or two eggmasses.

The test compounds were formulated by diluting the stock suspension withwater to give a suspension containing 500 parts of test compound permillion parts of final formulation. The egg masses were dipped untilthey were thoroughly wet (5-10 seconds). They were then placed on apaper towel face up and were allowed to dry for 15-30 minutes. The dryeggs were placed in a 15×60 mm petri dish containing a cotton dentalwick saturated with a 5 percent sodium chloride solution to maintain ahigh level of humidity. The closed dishes were labeled and held at atemperature of 80°±5° F. for four days. Larvae that emerged from theeggs, even if dead at the time of observation, were recorded as hatched.

Mite Foliage Spray Test

Adults and nymphal stage of the two-spotted mite (Tetranychus urticaeKoch), reared on Tendergreen bean plants at 80±5 percent relativehumidity, were the test organisms. Infested leaves from a stock culturewere placed on the primary leaves of two bean plants six to eight inchesin height, growing in a two-and-a-half inch clay pot. 150-200 mites, asufficient number for testing, were transferred from the excised leavesto the fresh plants in a period of twenty-four hours. Following thetwenty-four hour transfer period, the excised leaves were removed fromthe infested plants. The test compounds were formulated by diluting thestock suspension with water to give a suspension containing 500 parts oftest compound per million parts of final formulation. The potted plants(one pot per compound) were placed on a revolving turntable and sprayedwith 100-110 milliliters of test compound formulation by use of aDeVilbiss spray gun set at 40 psig. air pressure. This application,which last 25 seconds, was sufficient to wet the plants to run-off. As acontrol, 100-110 milliliters of a water solution containing acetone andemulsifier in the same concentrations as the test compound formulations,but containing no test compound, were also sprayed on infested plants.The sprayed plants were held at 80±5 percent relative humidity for sixdays, after which a mortality count of motile forms was made.Microscopic examination for motile forms was made on the leaves of thetest plants. Any individual which was capable of locomotion uponprodding was considered living.

Fly Bait Test

Four to six day old adult house flies (Musca domestica, L.), rearedaccording to the specifications of the Chemical SpecialtiesManufacturing Association (Blue Book, McNair-Dorland Co., N.Y. 1954;pages 243-244, 261) under controlled conditions of 80°±5° F. and 50±5percent relative humidity, were the test insects. The flies wereimmobilized by anesthetizing with carbon dioxide and twenty-fiveimmobilized individuals, males and females, were transferred to a cageconsisting of a standard food strainer about five inches in diameterwhich was inverted over a wrapping-paper-covered surface. The testcompounds were formulated by diluting the stock suspension with a 10percent (by weight) sugar solution to give a suspension containing 500parts of test compound per million parts of final formulation, byweight. Ten milliliters of the test formulation were added to a soufflecup containing a one-inch square of an absorbent cotton pad. This baitcup was introduced and centered on the blotting paper under the goodstrainer prior to admitting the anesthetized flies. The caged flies wereallowed to feed on the bait for twenty-four hours, at a temperature of80±5° F. and a relative humidity of 50±5 percent. Flies which showed nosign of movement on prodding were considered dead.

The results of these tests together with physical properties of thetested compounds are set forth in Table I below. In these tests thepesticidal activity of the compounds at the indicated dosage rateagainst aphid, mite, Southern Armyworm, Bean Beetle, and housefly wasrated as follows:

A=excellent control

B=partial control

C=no control at 500 ppm.

The compounds contemplated in this invention may be applied asinsecticides and miticides according to methods known to those skilledin the art. Pesticidal compositions containing the compounds as theactive toxicant will usually comprise a carrier and/or diluent, eitherliquid or solid.

Suitable liquid diluents or carriers include water, petroleumdistillates, or other liquid carriers with or without surface activeagents. Liquid concentrates may be prepared by dissolving one of thesecompounds with a nonphytotoxic solvent such as acetone, xylene, ornitrobenzene and dispersing the toxicants in water with the acid ofsuitable surface active emulsifying and dispersing agents.

The choice of dispersing and emulsifying agents and the amount employedis dictated by the nature of the composition and ability of the agent tofacilitate the dispersion of the toxicant. Generally, it is desirable touse as little of the agent as is possible, consistent with the desireddispersion of the toxicant in the spray so that rain does notre-emulsify the toxicant after it is applied to the plant and wash itoff the plant. Non-ionic, anionic, amphoteric, or cationic dispersingand emulsifying agents may be employed, for example, the condensationproducts of alkylene oxides with phenol and organic acids, alkyl arylsulfonates, complex ether alcohols, quaternary ammonium compounds, andthe like.

In the preparation of wettable powder, dust or granulated compositions,the active ingredient is dispersed in and on an appropriately dividedsolid carrier such as clay, talc, bentonite, diatomaceous earth, fullersearth, and the like. In the formulation of the wettable powders theaforementioned dispersing agents as well as lignosulfonates can beincluded.

The required amount of the toxicants contemplated herein may be appliedper acre treated in from 1 to 200 gallons or more of liquid carrierand/or diluent or in from about 5 to 500 pounds of inert solid carrierand/or diluent. The concentration in the liquid concentrate will usuallyvary from about 10 to 95 percent by weight and in the solid formulationsfrom about 0.5 to about 90 percent by weight. Satisfactory sprays,dusts, or granules for general use contain from about 1/4 to 15 poundsof active toxicant per acre.

The pesticides contemplated herein control the population of insects,mites and of ova mites and insects upon plants or other material towhich the pesticides are applied. Generally, when used in sufficientamount to kill or repel the insects, they do not burn or injure theplant. The toxicants are compatible with substantially any otherconstituents of the spray schedule, and they may be used in the soil,upon the seeds, or the roots of plants without injuring either the seedsor roots of plants. They may also be used in combination with otherpesticidally active compounds.

    TABLE I      Biological and Analytical Properties of the Compounds of this Invention S     TRUCTURE      ##STR7##       BIOLOGICAL ACTIVITYSOUTHERNMEXICAN R.sup.1 R.sup.2 R.sup.3 ANALYTICAL     BEAN APHID MITE ADULT ARMY WORM BEAN BEETLE HOUSEFLY       4-CHNNHCONH.sub.2 H H C.sub.13 H.sub.20 N.sub.3 O.sub.4 PS B A A A A      Calc: C, 45.21; H, 5.85    Found: C, 45.39; H, 5.77    mp (°C.):     118.5-122 2-CHNNHCOCONH.sub.2 H H C.sub.14 H.sub.20 N.sub.3 O.sub.5 PS C     A A A A    Calc: C, 45.04; H, 5.41    Found: C, 45.33; H, 5.44    mp     (°C.): 148-150.5 2-CHNOCH.sub.3 H H C.sub.13 H.sub.20 NO.sub.4 PS     A A A A A    Calc: C, 49.20; H, 6.36    Found: C, 49.63; H, 6.52    OIL     3-CHNNHCONH.sub.2 H H C.sub.13 H.sub.20 N.sub.3 O.sub.4 PS C A A A A     Calc: C, 45.21; H, 5.85    Found: C, 47.13; H, 6.55    OIL 2-CHNNHCOCH.su     b.3 H H C.sub.14 H.sub.21 N.sub.2 O.sub.4 PS C A A A A    Calc: C,     48.83; H, 6.16    Found: C, 48.80; H, 6.17    OIL 2-CHNNHCOCH.sub.2 CN H     H C.sub.15 H.sub.20 N.sub.3 O.sub.4 PS C A A A A    Calc: C, 48.80; H,     5.47    Found: C, 48.05; H, 5.58    mp (°C.): 103-110      ##STR8##      H H C.sub.17 H.sub.21 N.sub.2 O.sub.5 PSCalc: C, 51.51; H, 5.35Found:     C, 50.59; H, 4.52Oil C A A A A  2-CH NNHCO.sub.2 CH.sub.2 CH.sub.3 H H     C.sub.15 H.sub.23 N.sub.2 O.sub.4 PS A A A A A    Calc: C, 48.12; H,     6.20    Found: C, 44.92; H, 6.44    Oil 2-CHNNHCONH.sub.2 4-Cl H     C.sub.13 H.sub.19 ClN.sub.3 O.sub.4 PS B A A A A    Calc: C, 41.11; H,     5.05    Found: C, 41.67; H, 4.94    mp (°C.): 112-116 2-CHNNHCONH.     sub.2 4-NO.sub.2 H C.sub.13 H.sub.14 N.sub.4 O.sub.6 PS B A A A A     Calc: C, 40.00; H, 4.92    Found: C, 38.24; H, 4.78    mp (°C.):     105-109.5 4-CHNNHCONH.sub.2 2-OCH.sub.3 H C.sub.14 H.sub.22 N.sub.3     O.sub.3 PS C C A A A    Calc: C, 44.79; H, 5.91    Found: C, 44.99; H,     5.87    mp (°C.): 133-138 4-CHNOCH.sub.3 H H C.sub.13 H.sub.20     NO.sub.4 PS A A A A A    Calc: C, 49.20; H, 6.35    Found: C, 49.35; H,     6.42    Oil 3-CHNNHCONH.sub.2 4-NO.sub.2 H C.sub.13 H.sub.19 N.sub.4     O.sub.6 PS C A A A A    Calc: C, 40.00; H, 4.91    Found: C, 38.5; H,     4.67    mp (°C.): 128-131 4-CHNNHCONH.sub.2 2-NO.sub.2 6-OCH.sub.3      C.sub.14 H.sub.21 N.sub.4 O.sub.7 PS A A A A A    Calc: C, 40.00; H,     5.04    Found: C, 39.30; H, 5.26    mp (°C.): 149-154 2-CHNNHCO.su     b.2 CH.sub.3 H H C.sub.14 H.sub.21 N.sub.2 O.sub.5 PS A A A A A    Calc:     C, 46.66; H, 5.88    Found: C, 46.72; H, 6.38    OIL 2-CHNNHCO.sub.2     C(CH.sub.3).sub.3 H H C.sub.17 H.sub.27 N.sub.2 O.sub.5 PS A C A A A     Calc: C, 50.73; H, 6.76    Found: C, 49.49; H, 7.20    OIL 2-CHO     4-NO.sub.2 H C.sub.12 H.sub.16 NO.sub.6 PS A A A A A    Calc: C, 43.24;     H, 4.85    Found: C, 42.53; H, 5.23    OIL 3-CHO 4-NO.sub.2 H C.sub.12     H.sub.16 NO.sub.6 PS A A A A A    Calc: C, 43.25; H, 4.84    Found: C,     40.98; H, 4.95    OIL 4-CHO 2-NO.sub.2 6-OCH.sub.3 C.sub.13 H.sub.18     NO.sub.7      PS A A A A A    Calc: C, 42.98; H, 5.00    OIL 4-CHO 2-OCH.sub.3 H     C.sub.13 H.sub.19 O.sub.5 PS A A A B A    Calc: C, 49.05; H, 6.03     Found: C, 47.23; H, 6.17    OIL 2-CHO 4-OCH.sub.3 H C.sub.13 H.sub.19     O.sub.5 PS A A A A A    Calc: C, 49.05; H, 6.03    Found: C, 48.49; H,     6.10    OIL      2-CHO     ##STR9##       C.sub.16 H.sub.19 O.sub.4 PSCalc: C, 56.80; H, 5.67Found: C, 56.41; H,     5.95OIL A A A A A      2-CHNNHCONH.sub.2     ##STR10##       C.sub.17 H.sub.22 N.sub.3 O.sub.4 PSCalc: C, 51.65; H, 5.57Found: C,     52.33; H, 5.54OIL C A A A A  2-CHNNHCONH.sub.2 H H C.sub.13 H.sub.20     N.sub.2 OPS C A A A A    Calc: C, 45.22; H, 5.80    Found: C, 45.36; H,     5.72    mp (°C.): 127-129      2-CHO     ##STR11##       C.sub.17 H.sub.21 O.sub.4 PS (Sn-butyl)Calc: C, 57.94; H, 4.86Found:     C, 57.04; H, 6.18OIL A A A A A  2-CHNNHCSNH.sub.2 H H C.sub.13 H.sub.20     N.sub.3 O.sub.3 PS.sub.2 C A A B A    Calc: C, 43.70; H, 5.58    Found:     C, 44.64; H, 5.51    OIL      ##STR12##      H H C.sub.17 H.sub.29 ClN.sub.3 O.sub.4 PS Calc: C, 46.63; H, 6.63OIL C     A A C A  4-CHNOCH.sub.3 2-Cl 6-Cl C.sub.13 H.sub.18 Cl.sub.2 NO.sub.4 PS     A A A A A    Calc: C, 40.43; H, 4.71    Found: C, 40.72; H, 4.69    OIL     4-CHNNHCONH.sub.2 2-Cl 6-Cl C.sub.13 H.sub.17 Cl.sub.2 N.sub.3 O.sub.4     PS A A A A A    Calc: C, 37.78; H, 4.16    Found: C, 37.72; H, 4.15     mp (°C.): 130-133 4-CHNNHCO.sub.2 CH.sub.3 2-Cl 6-Cl C.sub.14     H.sub.19 Cl.sub.2 N.sub.2 O.sub.5 PS B A A A A    Calc: C, 39.17; H,     4.47    Found: C, 37.76; H, 4.50    mp (°C.): 83-85 2-CHNNHCO.sub.     2 CH.sub.3 4-NO.sub.2 H C.sub.14 H.sub.19 N.sub.3 O.sub.7 PS C A A A A      Calc: C, 41.48; H, 4.73    Found: C, 41.21; H, 4.99    mp (°C.):     92-95 2-CHNNHCO.sub.2 CH.sub.3 4-Cl H C.sub.14 H.sub. 20 ClN.sub.2     O.sub.5 PS B A A A A    Calc: C, 42.59; H, 5.11    Found: C, 42.48; H,     5.03    mp (°C.): 98-103 2-CHNOCH.sub.3 4-NO.sub.2 H C.sub.13     H.sub.19 N.sub.2 O.sub.6 PS A A A A A    Calc: C, 43.09; H, 5.30     Found: C, 43.89; H, 5.40    OIL 4-CHNNHCSNHCH.sub.2 CHCH.sub.2 H H     C.sub.16 H.sub.24 N.sub.3 O.sub.3 PS.sub.2 C A A A A    Calc: C, 47.86;     H, 6.03    Found: C, 48.12; H, 6.12    OIL 2-CHNNHCO.sub.2 CH.sub.3     4-OCH.sub.3 H C.sub.15 H.sub.23 N.sub.2 O.sub.6 PS C A A A A    Calc: C,     46.14; H, 5.95    Found: C, 45.00; H, 6.51    OIL 2-CHNNHCOCH.sub.3     4-OCH.sub.3  C.sub.15 H.sub.23 N.sub.2 O.sub.5 PS A A A A A    Calc: C,     48.11; H, 6.20    Found: C, 47.37; H, 6.27    mp (°C.): 75-78     N     2-CHNHCONH.sub.2 4-OCH.sub.3 H C.sub.14 H.sub.22 N.sub.3 O.sub.5 PS C A     A A A    Calc: C, 44.79; H, 5.91    Found: C, 45.52; H, 5.93    mp     (°C.): 113-117 4-CHNOCH.sub.2 C.sub.6 H.sub.5 H H C.sub.19     H.sub.24 NO.sub.4 PS A A A A A    Calc: C, 58.00; H, 6.16    Found: C,     57.60; H, 5.82    OIL 2-CHNOCH.sub.3 4-OCH.sub.3 H C.sub.14 H.sub.22     NO.sub.5 PS A A A A A    Calc: C, 48.41; H, 6.39    Found: C, 51.39; H,     6.98    OIL 4-CHNNHCONH.sub.2 2-Br 6-Br C.sub.13 H.sub.18 Br.sub.2     N.sub.3 O.sub.4 PS A A A A A    Calc: C, 31.03; H, 3.61    Found: C,     31.06; H, 3.55    mp (°C.): 155-156 4-CHNNHCO.sub.2 CH.sub.3 2-Br     6-Br C.sub.14 H.sub.19 Br.sub.2 N.sub.2 O.sub.5 PS C A A A A    Calc: C,     32.45; H, 3.70    Found: C, 33.63; H, 3.80    OIL 4-CHNOCH.sub.3 2-Br     6-Br C.sub.13 H.sub.18 Br.sub.2 NO.sub.4 PS A A A A A    Calc: C, 32.86;     H, 3.83    Found: C, 33.13; H, 3.88    OIL      ##STR13##      H H C.sub.19 H.sub.22 Cl.sub.2 NO.sub.4 PSCalc: C, 49.35; H, 4.81Found:     C, 49.38; H, 4.88OIL A A A A A      ##STR14##      H H C.sub.19 H.sub.22 Cl.sub.2 NO.sub.4 PSCalc: C, 49.35; H, 4.81Found:     C, 49.42; H, 4.91OIL A A A A A      ##STR15##      2-Cl 6-Cl C.sub.19 H.sub.20 Cl.sub.4 NO.sub.4 PSCalc: C, 42.96; H,     3.80Found: C, 42.89; H, 3.91 OIL A A A A A  4-CHC(CN).sub.2 H H C.sub.15     H.sub.17 N.sub.2 O.sub.3 PS C A A A A    Calc: C, 53.56; H, 5.10     Found: C, 51.02; H, 5.11    mp (°C.): 60-70 2-CHNOCH.sub.3 4-Cl H     C.sub.13 H.sub.19 ClNO.sub.4 PS A A A A A    Calc: C, 44.38; H, 5.45     Found: C, 44.60; H, 5.90    OIL 2-CHNNHCOCH.sub.3 4-NO.sub.2 H C.sub.14     H.sub.20 N.sub.3 O.sub.6 PS A A A A A    Calc: C, 43.19; H, 5.19     Found: C, 43.39; H, 5.40    mp (°C.): 157-160 2-CHNNHCOCH.sub.3     4-Cl H C.sub.14 H.sub.20 ClN.sub.2 O.sub.4 PS A A A A A    Calc: C,     44.43; H, 5.34    Found: C, 44.68; H, 5.25    mp (°C.): 105-108     4-CHNNHCOCONH.sub.2 H H C.sub.14 H.sub.20 N.sub.3 O.sub.5 PS C A A A A      Calc: C, 45.03; H, 5.41    Found: C, 44.28; H, 5.33    mp (°C.):     218-220 4-CHNNHCO.sub.2 CH.sub.3 H H C.sub.14 H.sub.21 N.sub.2 O.sub.5     PS B A A A A    Calc: C, 46.66; H, 5.88    Found: C, 46.91; H, 6.03     OIL      2-CHNOCH.sub.3     ##STR16##       C.sub.17 H.sub.22 NO.sub.4 PSCalc: C, 55.57; H, 6.04Found: C, 56.66;     H, 6.02OIL A A A A A

In Table II, Examples A through C are compounds found in the prior art.Examples D through F, are compounds of this invention. Comparisons ofthe pesticidal properties of each are illustrative of the surprisinglyand significantly enhanced effectiveness achieved with the utilizationof the compounds of this invention.

Similarly, comparisons of the prior art compound of Example G of TableII to Examples H and I--compounds of this invention--illustratively showthe increased pesticidal effectiveness realized with the compounds ofthis invention.

                                      TABLE II                                    __________________________________________________________________________                                 BIOLOGICAL ACTIVITY LD.sub.50 (ppm)                                                     SOUTHERN                                                                              MEXICAN                                                     BEAN MITE ARMY    BEAN                           EX.                                                                              STRUCTURE                 APHID                                                                              ADULT                                                                              WORM    BEETLE  HOUSEFLY               __________________________________________________________________________        ##STR17##                70   25   80      500     130                    B                                                                                 ##STR18##                15   i    108     i       58                     C                                                                                 ##STR19##                200  32   300     500     450                    D                                                                                 ##STR20##                i    4    7       46      9                      E                                                                                 ##STR21##                i    3    9       15      9                      F                                                                                 ##STR22##                180  1    16      20      16                     G                                                                                 ##STR23##                25   12   105     150     30                     H                                                                                 ##STR24##                20   20   20      12      13                     I                                                                                 ##STR25##                500  3    12      15      7                      __________________________________________________________________________

We claim:
 1. A method of controlling insects and mites which comprisessubjecting them to an insecticidally or miticidally effective amount ofa compound of the formula: ##STR26## wherein: X is oxygenR¹ and R² areindividually lower alkyl groups; Z is hydrogen, alkyl, alkoxy, halo,nitro, cyano, aryl, aryloxy, alkylthio, amino, alkylamino, dialkylamino,a C₃ to C₈ cycloalkyl, alkylthioalkyl, alkylsulfinylalkyl,alkylsulfonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, trihaloalkyl, ordivalent alkylene group of 3 to 5 carbon atoms; n is 1, 2 or 3; Y is##STR27## wherein: R³ and R⁴ are individually hydrogen, lower alkyl,lower alkenyl, or aryl;
 3. NOR⁵ wherein: R⁵ is substituted orunsubstituted lower alkyl, aryl, or arylalkyl; ##STR28## wherein: R⁶ islower alkyl, alkoxy, aryloxy, substituted alkyl, cycloalkoxy, furanyl,or phenylureido; ##STR29## wherein: R⁹ is lower alkyl;wherein: X¹ isoxygen or sulfur.
 2. A method in accordance with claim 1 wherein thecompoundisO-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphate. 3.A method in accordance with claim 1 wherein the compoundisO-ethyl-S-n-propyl-O-[2-(acetylhydrazonomethyl)phenyl]thiophosphate.4. A method in accordance with claim 1 wherein the compoundisO-ethyl-S-n-propyl-O-[2-(methoxycarbonyl-hydrazonomethyl)phenyl]thiophosphate.5. A method in accordance with claim 1 wherein the compoundisO-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminomethyl)phenyl]thiophosphate.6. A method in accordance with claim 1 wherein the compoundisO-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semi-carbazonomethyl)phenyl]thiophosphate.7. A method in accordance with claim 1 wherein the compoundisO-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyloxyiminomethyl)phenyl]thiophosphate.8. A method in accordance with claim 1 wherein the compoundisO-ethyl-S-n-propyl-O-[2,6-dibromo-4-(methoxyiminomethyl)phenyl]thiophosphate.9. A method of controlling insects and mites which comprises subjectingthem to an insecticidally or miticidally effective amount of a compoundof the formula: ##STR30## wherein: X is oxygen or sulfur;R¹ and R² areindividually lower alkyl groups; Z is a substituted or unsubstituted 4carbon, divalent alkylene group forming a 6-membered aromatic ring; n is1, 2 or 3; Y is ##STR31## wherein: R³ and R⁴ are individually hydrogen,lower alkyl, lower alkenyl, or aryl;
 3. NOR⁵ wherein: R⁵ is substitutedor unsubstituted lower alkyl, aryl, or arylalkyl; ##STR32## wherein: R⁶is lower alkyl, alkoxy, aryloxy, substituted alkyl, cycloalkoxy,furanyl, or phenylureido; ##STR33## wherein: R⁹ is lower alkyl;wherein:X¹ is oxygen or sulfur.
 10. A method of controlling insects and miteswhich comprises subjecting them to an insecticidally and miticidallyeffective amount of a compound of the formula: ##STR34## wherein: X isoxygen;R¹ is ethyl; R² is n-propyl; Z is hydrogen, a 4-carbon divalentalkylene group forming a 6-membered aromatic ring, or halo; n is 1, 2 or3; Y is ##STR35##
 11. A method in accordance with claim 9 wherein thecompoundisO-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)-2-naphthyl]-thiophosphate.12. Compounds of the formula: ##STR36## wherein: X is oxygen orsulfur;R¹ and R² are individually lower alkyl groups; Z is hydrogen,alkyl, alkoxy, halo, nitro, cyano, aryl, aryloxy, alkylthio, amino,alkylamino, dialkylamino, a C₃ to C₈ cycloalkyl, alkylthioalkyl,alkylsulfinylalkyl, alkylsulfonylalkyl, alkylaminoalkyl, or divalentalkylene group of 3 to 5 carbon atoms; n is 1, 2 or 3; Y is ##STR37##wherein: R³ and R⁴ are individually hydrogen, lower alkyl, loweralkenyl, or aryl;
 3. NOR⁵ wherein: R⁵ is substituted or unsubstitutedlower alkyl, aryl, or arylalkyl; ##STR38## wherein: R⁶ is lower alkyl,alkoxy, aryloxy, substituted alkyl, cycloalkoxy, furanyl, orphenylureido; ##STR39## wherein: R⁹ is lower alkyl;wherein X¹ is oxygenor sulfur. 13.O-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)-2-naphthyl]thiophosphate.14. O-ethyl-S-n-propyl-O-[2-(semicarbazonomethylphenyl]thiophosphate.15. O-ethyl-S-n-propyl-O-[2-(acetylhydrazonomethyl)phenyl]thiophosphate.16.O-ethyl-S-n-propyl-O-[2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate.17.O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminomethyl)phenyl]thiophosphate18.O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosphate.19.O-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyloxyiminomethyl)phenyl]thiophosphate.20.O-ethyl-S-n-propyl-O-[2,6-dibromo-4-(methoxyiminomethyl)phenyl]thiophosphate.21. Compounds of the formula: ##STR40## wherein: X is oxygen orsulfur;R¹ and R² are individually lower alkyl groups; Z is a substitutedor unsubstituted 4 carbon, divalent alkylene group forming a 6-memberedaromatic ring; n is 1,2 or 3; Y is ##STR41## wherein R³ and R⁴ areindividually hydrogen, lower alkyl, lower alkenyl, or aryl;
 3. NOR⁵wherein: R⁵ is substituted or unsubstituted lower alkyl, aryl, orarylalkyl; ##STR42## wherein: R⁶ is lower alkyl, alkoxy, aryloxy,substituted alkyl, cycloalkoxy, furanyl, or phenylureido; ##STR43##wherein: R⁹ is lower alkyl;wherein: X¹ is oxygen or sulfur. 22.Compounds of the formula: ##STR44## wherein: X is oxygen;R¹ is ethyl; R²is n-propyl; Z is hydrogen, a 4-carbon, divalent alkylene group forminga 6-membered aromatic ring, or halo; n is 1, 2, or 3; and Y is ##STR45####STR46## or NOCH₃.
 23. An insecticidal and miticidal compositioncomprising an acceptable carrier and as the active toxicant, apesticidally effective amount of a compound of the formula. ##STR47##wherein; X is oxygen or sulfur,R¹ and R² are individually lower akylgroups, Z is hydrogen, alkyl, alkoxy, halo, nitro, cyano, aryl, aryloxy,alkylthio, amino, alkylamino, dialkylamino, a C₃ to C₈ cycloalkyl,alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylaminoalkyl,dialkylaminoalkyl, trihaloalkyl, or divalent alkylene group of 3 to 5carbon atoms; n is 1, 2 or 3; Y is ##STR48## wherein: R³ and R⁴ areindividually hydrogen, lower alkyl, lower alkenyl or aryl;
 3. NOR⁵wherein: R⁵ is substituted or unsubstituted lower alkyl, aryl, orarylalkyl; ##STR49## wherein: R⁶ is lower alkyl, alkoxy, aryloxy,substituted alkyl, cycloalkoxy, furanyl, or phenylureido; ##STR50##wherein: R⁹ is lower alkyl;wherein: X¹ is oxygen or sulfur.
 24. Acomposition in accordance with claim 23 wherein the active toxicantisO-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl), phenyl]thiophosphate.25. A composition in accordance with claim 23 wherein the activetoxicantisO-ethyl-S-n-propyl-O-[2-(acethylhydrazonomethyl)phenyl]thiophosphate.26. A composition in accordance with claim 23 wherein the activetoxicantisO-ethyl-S-n-propyl-O-[2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate.27. A composition in accordance with claim 23 wherein the activetoxicantisO-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminomethyl)phenyl]thiophosphate.28. A composition in accordance with claim 23 wherein the activetoxicantisO-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosphate.29. A composition in accordance with claim 23 wherein the activetoxicantisO-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyl-oxyiminomethyl)phenyl]thiophosphate.30. A composition in accordance with claim 23 wherein the activetoxicantisO-ethyl-S-n-propyl-O-[2,6-dibromo-4-(methoxyiminomethyl)phenyl]thiophosphate.31. An insecticidal and miticidal composition comprising an acceptablecarrier and as the active toxicant, a pesticidally effective amount of acompound of the formula: ##STR51## wherein: X is oxygen or sulfur,R¹ andR² are individually lower alkyl groups, Z is a substituted orunsubstituted 4 carbon, divalent alkylene group forming a 6-memberedaromatic ring; n is 1, 2 or 3; Y is ##STR52## wherein: R³ and R⁴ areindividually hydrogen, lower alkyl, lower alkenyl or aryl;
 3. NOR⁵wherein: R⁵ is substituted or unsubstituted lower alkyl, aryl, orarylalkyl; ##STR53## wherein: R⁶ is lower alkyl, alkoxy, aryloxy,substituted alkyl, cycloalkoxy, furanyl, or phenylureido: ##STR54##wherein: R⁹ is lower alkyl;wherein: X¹ is oxygen or sulfur.
 32. Aninsecticidal and miticidal composition comprising an acceptable carrierand as the active toxicant, a pesticidally effective amount of acompound of the formula: ##STR55## wherein: X is oxygen;R¹ is ethyl R²is n-propyl; Z is hydrogen, a 4 carbon, divalent alkylene group forminga 6-membered aromatic ring, or halo; n is 1, 2 or 3; Y is ##STR56## 33.A composition in accordance with claim 31 wherein the active toxicantisO-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)2-naphthyl]thiophosphate.